Method of tracing flow of hydrocarbon from a subterranean reservoir

ABSTRACT

A method of tracing flow of hydrocarbon from a subterranean reservoir including forming a dispersion, injecting a hydraulic fracturing fluid containing the dispersion down a well penetrating a hydrocarbon reservoir, thereafter collecting a sample of hydrocarbon fluid flowing from the reservoir, and analysing the sample to determine whether the tracer compound is present in the sample. The dispersion includes a discontinuous condensed phase having a hydrocarbon-soluble tracer compound and a continuous phase which includes an aqueous liquid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/169,679, filed Jan. 31, 2014 and allowed on Nov. 4, 2015, which is acontinuation of U.S. patent application Ser. No. 13/918,527, filed Jun.14, 2013 and issued on Feb. 4, 2014 with Pat. No. 8,640,773, which is acontinuation of U.S. patent application Ser. No. 13/645,778, filed Oct.5, 2012, and claims priority of Provisional Patent Application No.61/543,359, filed Oct. 5, 2011, the disclosures of which areincorporated herein by reference in their entireties for all purposes.

FIELD OF INVENTION

The present invention relates to a method of tracing the flow ofhydrocarbons from a subterranean reservoir following a hydraulicfracturing operation.

BACKGROUND OF THE INVENTION

The development of “tight” oil and gas from within geological strata oflow permeability has increased dramatically over the past few years dueto advances in drilling and completion technologies that allow operatorsto create geological flow through the use of multi stage hydraulicfracturing operations in highly deviated or horizontal wells. Thisinvolves the construction of a completion arrangement that allowsspecific vertically deviated or horizontal sections of a well bore to beisolated and hydraulically fractured. Repeating this process along thelength of the well bore in the target reservoir area ensures thatcontrolled hydraulic fracturing of every potential flow-contributingzone is achieved.

Once the hydraulic fracturing has been completed, previously injectedfluid as well as hydrocarbons present within the formation surroundingthe wellbore are allowed to flow to the surface from deep within thesubsurface strata. Currently the logging of these “extended reach” wellsis not routinely carried out as it is expensive, time consuming and canbe relatively inaccurate when attempted in a long horizontal well bore.However, operators wish to better understand the effectiveness ofspecific hydraulic fracture project design in extracting trapped oil orgas from reservoir zones in order that they can improve design forfuture development wells.

In the oil and gas exploration and production industry it is common tohydraulically fracture a hydrocarbon-containing rock formation, orreservoir, in order to allow the hydrocarbon to flow out of the rockthrough the rock fractures. Many methods of fracturing a rock formationand maintaining a fracture open for the flow of hydrocarbon are knownand practised in the industry. It is also known in the art to trace theflow of fluids from a reservoir, including fluids flowing after afracturing operation, using tracers. For example, European Patent Number1991759 describes a method of monitoring the flow of fluid within orfrom a reservoir comprising the steps of inserting a solidnon-radioactive tracer into the reservoir by means of a perforationtool, thereafter collecting a sample of fluid within or flowing from thereservoir and analysing said sample to determine the amount of saidtracer contained in the sample. From the presence or absence of tracerin the sample, its amount and other parameters such as timing of thesample collection etc., information about the fluid flow within thereservoir may be gathered. U.S. Pat. No. 3,623,842 describes a method ofdetermining fluid saturations in reservoirs by injecting at least twotracers having different partition coefficients between fluid phases(e.g. oil and water) into the formation and monitoring the appearance ofthe two tracers in the produced fluids. Radioactive tracers have beenwidely used for many years in well-monitoring applications. As anexample, see U.S. Pat. No. 5,077,471, in which radioactive tracers areinjected into a perforated well-bore, sealed and then monitored fordecay to indicate the fluid flow from the formation. U.S. Pat. No.4,755,469 describes the use of rare metal tracers for tracing oil andassociated reservoir fluids by mixing an oil-dispersible rare metal saltwith oil or an oil-like composition, injecting the dissolved tracercomposition into a subterranean reservoir and analysing oil fluidsproduced from a different part of the reservoir for the presence of therare metal to determine whether the oil mixed with the tracer has beenproduced from the reservoir.

SUMMARY OF THE INVENTION

We have found that the application of hydrocarbon-partitioning tracertechnology can be used to overcome some of the problems encountered inwell-logging operations of highly deviated or horizontal wells subjectedto hydraulic fracture stimulation.

In one embodiment of the invention, we provide a method of tracing flowof hydrocarbon from a subterranean reservoir comprising the steps offorming a dispersion consisting of a discontinuous condensed phase and acontinuous liquid phase, said discontinuous condensed phase comprising ahydrocarbon-soluble tracer compound and said continuous liquid phasecomprising an aqueous liquid; injecting a hydraulic fracturing fluidcontaining the dispersion down a well penetrating a hydrocarbonreservoir; thereafter collecting a sample of hydrocarbon fluid flowingfrom the reservoir and analysing the sample to determine whether thetracer compound is present in the sample.

In a second embodiment of the invention, the method of tracing flow ofhydrocarbon from a subterranean reservoir comprises the steps of formingat least two tracer emulsions, each tracer emulsion comprising an oil orgas-soluble tracer compound in water and having a tracer characteristicwhich is different from the corresponding tracer characteristic of eachother tracer emulsion, injecting a hydraulic fracture fluid containingat least one of said emulsions down a well penetrating a hydrocarbonreservoir, thereafter collecting a sample of hydrocarbon flowing fromthe reservoir and analysing the sample to determine whether any of thetracer compounds is present in the sample.

The methods are useful for identifying a part of the well from which theflow of hydrocarbon has originated, and may also be used to identifyflow of reservoir fluids through plugs which have been placed in a well.It is usual to restrict the flow of fluids from selected parts of a wellat various times during production by the placement of plugs whichrestrict or prevent flow of fluids downstream past the plug. When flowis to be restarted, one or more plugs are released to provide a passagefor flow of fluids from locations upstream of the plug to locationsdownstream of the plug, for example to the well-head. The methods, suchas the first and second embodiments of the invention, may then be usedto confirm that the selected plugs have been released by providing amethod for identifying flow from parts of the well located upstream ofthe plug location.

We therefore further provide a method of confirming whether or not abarrier exists at a first location in a well which would, if present,restrict flow of a hydrocarbon from a location in a well upstream ofsaid first location to a location downstream of said first location,comprising the steps of forming an emulsion of an oil or gas-solubletracer compound in an aqueous liquid, injecting a hydraulic fracturefluid containing the emulsion down a well penetrating a hydrocarbonreservoir at said location upstream of said first location, thereaftercollecting a sample of hydrocarbon flowing from the reservoir at alocation downstream of said first location, analysing the sample todetermine whether the tracer compound is present in the sample andinferring from the presence or absence of tracer in the sample whethersaid sample contains hydrocarbon which has flowed from a locationupstream of said first location.

When practising the above method to confirm the release of a plug placedin the well, the method may further include taking action to remove thebarrier by releasing the plug after the tracer has been injected intothe well and before the sample is collected.

In a further embodiment of the invention we provide a method ofidentifying the flow of a hydrocarbon from a first location in asubterranean reservoir to a well located at a second location in saidreservoir comprising the steps of forming an emulsion of at least oneoil or gas-soluble tracer compound in an aqueous liquid, injecting ahydraulic fracture fluid containing the emulsion down a well penetratinga hydrocarbon reservoir at said first location, thereafter collecting asample of hydrocarbon flowing from the well located at said secondlocation, analysing the sample to determine whether the tracer compoundis present in the sample and identifying from the analytical results aflow of hydrocarbon from the first location to the second location.

This method is useful for identifying the flow of reservoir fluidsbetween wells, known as “cross-flow” and may provide information whichis useful to optimise the spacing of wells within a particular reservoiror formation.

We also provide compositions useful for carrying out the methods of theinvention, such compositions comprising a dispersion consisting of adiscontinuous condensed phase and a continuous liquid phase, thediscontinuous condensed phase comprising a hydrocarbon-soluble tracercompound and the continuous liquid phase comprising an aqueous liquid.The aqueous liquid may comprise a hydraulic fracturing fluid.

DETAILED DESCRIPTION OF THE INVENTION

The method of the invention is particularly effective for tracingpositional flow of hydrocarbon fluids from the reservoir.

The term “hydrocarbon” is intended to include all forms of oil andhydrocarbon gas normally extracted from subterranean hydrocarbonreservoirs. When we use the term “hydrocarbon” without indicatingwhether oil or gas is intended, we mean to include oil and hydrocarbongas. In this specification “gas” means hydrocarbon gas, e.g. natural gasunless any other kind of gas is specified. We use the term “dispersion”to mean a colloidal system having a discontinuous condensed (solid orliquid) phase incorporating a tracer compound and an aqueous liquidcontinuous phase. We use the term “emulsion” to mean adispersion havinga discontinuous liquid phase incorporating a tracer compound and anaqueous continuous phase.

The dispersion may comprise an emulsion, in which case the discontinuousphase comprises an organic liquid. The dispersion may alternativelycomprise a colloidal solids dispersion in which case the discontinuousphase comprises particles of a colloidal solid.

The tracer compound(s) are insoluble in water but soluble in oil or gasat the prevailing conditions in the reservoir. By “insoluble” we meanthat the solubility of the tracer between 50 degrees Celsius and 120degrees Celsius is less than 0.1 g/litre. By “soluble” we mean that thesolubility of the tracer between 50 degrees Celsius and 120 degreesCelsius is more than 100 g/litre. The tracer compounds are capable offorming a colloidal solids dispersion or an emulsion in a continuousaqueous phase, which is preferably either water, or a hydraulicfracturing fluid composition. Optionally, emulsifiers, rheologymodifiers and/or stabilisers may be included in the dispersion, in thediscontinuous tracer phase or the continuous aqueous phase. Interfacialstabilisers may be present at the boundary between the continuous phaseand the discontinuous phase. The dispersion is capable of being mixedwith a portion of a hydraulic fracturing fluid to the extent that itflows into the well with the fracturing fluid. The dispersion preferablyis added to the fracturing fluid and flows as a discrete slug in themain aqueous based fluid flow. The tracer compound is selected tosubstantially or fully partition into a hydrocarbon when the dispersioncomes into contact with oil and/or gas within the well or formation. Thepartition coefficient between the hydrocarbon/water) is thereforeselected to be at least 1,000 (Log P=3). The tracer compound may bedissolved in an organic solvent. In that case, the discontinuous phaseof the emulsion comprises a solution of the tracer compound in solvent.Suitable solvents include aromatic, cycloalkane or aliphatic chemicalssuch as petroleum distillates, examples of which include xylene,cyclohexane, or octane.

The tracer compound is preferably a halogenated aromatic, cycloalkane,or aliphatic compound including a halogen selected from the groupconsisting of Cl, Br and I. Suitable tracers include, but are notlimited to 4-iodotoluene, 1,4-dibromobenzene, 1-chloro-4-iodobenzene,5-iodo-m-xylene, 4-iodo-o-xylene, 3,5-dibromotoluene, 1,4-diiodobenzene,1,2-diiodobenzene, 2,4-dibromomesitylene, 2,4,6-tribromotoluene,1-iodonaphthalene, 2-iodobiphenyl, 9-bromophenanthrene,2-bromonaphthalene, bromocyclohexane, 1,2-dichlorobenzene,1,3-dichlorobenzene, 1,4-dichlorobenzene, 1-bromododecane, bromooctane,1-bromo-4-chlorobenzene, bromobenzene, 1,2,3-trichlorobenzene,4-chlorobenzylchloride, and 1-bromo-4-fluorobenzene.

The tracer compound is preferably a liquid or solid at room temperature.More than one tracer compound may be incorporated into the discontinuousphase of the dispersion. The dispersion may be formed prior to theinjection of fracturing fluid and then added to the hydraulic fracturingfluid injection during the fracturing operation. Alternatively thetracer compound itself, or a solution of the tracer in anon-water-miscible organic solvent, may be added to and mixed directlywith the hydraulic fracturing fluids during the injection, so that thedispersion is formed in situ, with the fracturing fluid forming thecontinuous aqueous phase of the dispersion. In either case, it ispreferred that a known amount of tracer is added to the fracturing fluidentering the well during each stage.

In order for the tracer dispersion to be useful in identifyinghydrocarbons flowing from a particular fracturing operation, it isimportant that it is introduced into the well in such a way that it canpenetrate the formation at the location of an induced fracture. Thetracer dispersion is preferably added to the fracturing fluidsintroduced into the well after the initial injection of fracture fluidcreating the initial rock fracture matrix. Preferably the tracerdispersion is added during the initial injection of solid proppantparticles, such as sand or ceramic proppant, during each stage, at thefront of the solids injection in order that it will enter deep into theformation and will contact hydrocarbon if present. It is preferred thatthe tracer is consistently injected at the same point during eachhydraulic stimulation stage. It is also preferred that the tracer is notinjected towards the end of the stage because in that case it may bevery close to the well bore and may flow back to surface whether or notit has contacted hydrocarbon.

A typical hydraulic fracturing operation in an oil or gas well iscarried out in stages, many using between 10 and 40 stages per well. Atracer dispersion may be added to each stage or only to some of thestages. The tracer used in each tracer dispersion is preferably unique,in that it preferably has a different tracer characteristic from eachother tracer compound used in the fracturing operation so thathydrocarbon flows produced from each stage may be identified. The tracercharacteristic is usually the chemical identity of the tracer compoundused. The tracer characteristic must be distinguishable from the tracercharacteristic(s) of any other tracer compounds used.

Following completion of the fracture work, the well is prepared for backflow. During the back flowing of the well, reservoir oil/gas samples aretaken on a regular basis, typically for the first 10 to 40 days. A smallamount of the sample is analysed using appropriate methods to detect thepresence and concentration of tracer compound. The method of analysingthe sample is selected to be useful to identify and, preferably, toprovide a measure of concentration of the tracer in the fluid sample.Suitable methods include chromatography; particularly gas chromatography(gc) coupled with appropriate detection means. Of particular use foridentifying and measuring the concentration of halogenated aromaticcompounds is gas chromatography coupled with mass spectrometry allowingdetection sensitivities to low parts per billion to be achievable.

The completion work may involve the plugging of a section of a well toprevent flow of fluid. This may be undertaken to block or control theflow of reservoir fluids from a certain part of the well, e.g. from thetoe of the well to towards the heel or surface. It may be useful toblock the flow of fracturing fluid at a particular location in the wellin order to fracture a particular part of the reservoir. The flow may beblocked, or restricted, e.g. as to direction or flow rate, by means of abarrier which can be in the form of a plug or a well completion device,such as a screen, having at least one flow control means comprising atleast one hole and which, in a first condition allows flow through saidhole and in a second condition blocks flow through said hole. Suchdevices may be operated to enable or block flow by means of a tool or bypressure built up in the well at the location of the barrier. Suchdevices are available as sliding sleeve arrangements for example. Whenthe barrier is a plug, for example filled with cement, the plug may bedrilled out in order to enable flow of fluid past the location of theplug. Operating a completion device to enable flow of fluid or drillingout a plug may be referred to as “releasing” the plug or barrier. In atypical well completion operation many such barriers to flow may beinstalled as the well is completed in stages. In a typical operation,each barrier may be associated with at least one reservoir fracturingoperation. Each fracturing operation is therefore convenientlyassociated with a particular tracer compound which is different fromtracer compounds used in other fracturing operations in the well. Whenthe method of the invention is used during a fracturing operation and abarrier, which has been placed downstream of the fracturing operation(for example to enable fracturing of another fracturing operationdownstream of the first (upstream) fracturing operation), is released orremoved, then the detection in a sample collected downstream of thebarrier location (e.g. at the well-head) of the tracer placed with theupstream fracturing operation confirms to the completion operator thatthe barrier has been released properly and that hydrocarbon fluid hasflowed from the reservoir at the upstream fracture past the location ofthe barrier.

It is preferred to record the amount of hydrocarbon produced by the wellover particular time periods during the period of taking samples fortracer analysis. In a particularly preferred method, concentrationversus time curves are created for each tracer. Integration of eachcurve over a specific period of time during flow back is carried out toprovide a profile of production from each fracture stage of the well. Acomparison of tracer flow back to surface versus the amount of traceremulsion injected at the surface is carried out versus time. Therecovery of each tracer may be compared using a normalization process todetermine the relative contribution of each stage over a specified timeperiod. This relative flow data is used to determine relative flow fromeach hydraulic stimulation stage to surface versus time.

DESCRIPTION OF DRAWINGS

FIG. 1A is a graph showing the % produced tracer in samples of oilcollected over 14 days from stages 1-8 in the Example.

FIG. 1B is a graph showing the % produced tracer in samples of oilcollected over 14 days from stages 9-16 in the Example.

FIG. 2 shows the variation in oil production between the stages over 14days.

FIG. 3 is a graph showing the cumulative amount of tracer in theproduced oil over 14 days.

EXAMPLE

A horizontal oil well was to be stimulated with a sixteen stagehydraulic fracture program evenly distributed along the well bore lengthat 300 feet intervals. An oil sample was taken from another well withinthe specific oilfield. A number of candidate organic tracers were mixedwith a suitable solvent and added to a water solution containingviscosity modifiers similar to those used during a hydraulic fracturingoperation and a small amount of emulsion promoter. The mixture wasblended to create a stable emulsion. Oil taken from the specificoilfield was added to the emulsion and each of the candidate organictracers' partition coefficients measured between the aqueous and organicphases. Sixteen unique organic tracers that formed stable emulsions andhad partition coefficients of 1,000 and above were selected for theproject. One of the sixteen unique organic based tracers was injected atthe leading edge of each hydraulic fracture stage when proppants werefirst added to the hydraulic fluids. The injected tracer formed anemulsion in the hydraulic fracturing fluid. The amount of tracerinjected into each stage was 250, 500 or 1000 grams. Tracer was notinjected into stage 3. Following completion of the stimulation treatmentthe well was cleaned and production started. Samples of oil werecollected on a regular basis and analysed for tracer presence. Resultsof the analysis are shown in FIGS. 1-3. FIG. 1A shows data for stages1-8 whilst stages 9-16 are shown in FIG. 1B. The results show thatinitial oil flow was dominated from stages closer to the heel of thewell with mid-point being relatively low and toe flow response from onlythe last two stages. The oil flow rate in barrels per hour is shown inFIGS. 1 and 3 as a bold dashed line. As flow continued, toe flow overallcontribution increased but mid-well flow continued to be relatively lowwith as many as 4 stages (Stages 3, 4, 6, and 10) contributing zero tothe overall production. This example shows that the contribution toproduction of each stage in the well can be analysed using the method ofthe invention.

1. A method of identifying the flow of reservoir fluids between a firstwell and a second well, the method comprising the steps of: a1) formingan emulsion of at least one hydrocarbon-soluble tracer compound in anaqueous liquid and injecting a hydraulic fracture fluid containing theemulsion down a first well, or a2) forming an emulsion of at least onehydrocarbon-soluble tracer compound in an aqueous liquid by adding thetracer compound or a solution of the tracer compound in a non-watermiscible solvent to a hydraulic fracturing fluid and mixing the traceror said solution of the tracer with hydraulic fracturing fluid duringinjection of the fracturing fluid down a first well, b) thereaftercollecting a sample of hydrocarbon flowing from the second well, c)analyzing the sample collected from the first well to determine whetherthe tracer compound is present in the sample from the second well and d)determining, from the results of said analysis, whether a flow ofhydrocarbon has occurred from the first well to the second well.
 2. Themethod of claim 1, where the emulsion comprises a discontinuous organicliquid phase and a continuous liquid phase, said discontinuous organicliquid phase comprising a hydrocarbon-soluble tracer compound and saidcontinuous liquid phase comprising an aqueous liquid.
 3. The method ofclaim 1, where the tracer compound substantially or fully partitionsinto a hydrocarbon within a reservoir into which the first well islocated when the dispersion comes into contact with oil and/or gaswithin the well or formation.
 4. A method according to claim 1 whereinthe tracer compound has a solubility in water between 50 and 120°Celsius of less than 0.1 g/liter.
 5. A method according to claim 1wherein the partition coefficient of the tracer compound between thehydrocarbon/water is selected to be at least 1,000.
 6. A methodaccording to claim 1 wherein the discontinuous organic liquid phase ofthe emulsion comprises a solution of the tracer compound in an organicsolvent.
 7. A method according to claim 1 wherein said emulsion containsan additive selected from the group consisting of emulsifiers,stabilisers and rheology modifiers.
 8. A method according to claim 1wherein the tracer compound is selected from the group consisting of ahalogenated aromatic compound, a halogenated cycloalkane and ahalogenated aliphatic compound, wherein the halogen is selected from thegroup consisting of Cl, Br and I.
 9. A method according to claim 8wherein the tracer compound is selected from the group consisting of4-iodotoluene, 1,4-dibromobenzene, 1-chloro-4-iodobenzene,5-iodo-m-xylene, 4-iodo-o-xylene, 3,5-dibromotoluene, 1,4-diiodobenzene,1,2-diiodobenzene, 2,4-dibromomesitylene, 2,4,6-tribromotoluene,1-iodonaphthalene, 2-iodobiphenyl, 9-bromophenanthrene,2-bromonaphthalene, bromocyclohexane, 1,2-dichlorobenzene,1,3-dichlorobenzene, 1,4-dichlorobenzene, 1-bromododecane, bromooctane,1-bromo-4-chlorobenzene, bromobenzene, 1,2,3-trichlorobenzene,4-chlorobenzylchloride and 1-bromo-4-fluorobenzene.
 10. A methodaccording to claim 1 wherein the discontinuous organic liquid phase ofthe emulsion contains more than one tracer compound.
 11. An emulsionconsisting of a discontinuous organic liquid phase and a continuousliquid phase, said organic liquid phase comprising a hydrocarbon-solubletracer compound and said continuous liquid phase comprising an aqueousliquid.
 12. An emulsion according to claim 11, wherein said emulsioncontains an additive selected from the group consisting of emulsifiers,stabilizers and rheology modifiers.
 13. An emulsion according to claim11, wherein the tracer compound is selected from the group consisting ofa halogenated aromatic compound, a halogenated cycloalkane or ahalogenated aliphatic compound, wherein the halogen is selected from thegroup consisting of Cl, Br and I.
 14. An emulsion according to claim 11,wherein the tracer compound is selected from the group consisting of4-iodotoluene, 1,4-dibromobenzene, 1-chloro-4-iodobenzene,5-iodo-m-xylene, 4-iodo-o-xylene, 3,5-dibromotoluene, 1,4-diiodobenzene,1,2-diiodobenzene, 2,4-dibromomesitylene, 2,4,6-tribromotoluene,1-iodonaphthalene, 2-iodobiphenyl, 9-bromophenanthrene,2-bromonaphthalene, bromocyclohexane, 1,2-dichlorobenzene,1,3-dichlorobenzene, 1,4-dichlorobenzene, 1-bromododecane, bromooctane,1-bromo-4-chlorobenzene, bromobenzene, 1,2,3-trichlorobenzene,4-chlorobenzylchloride and 1-bromo-4-fluorobenzene.
 15. An emulsionaccording to claim 11, wherein the at least one hydrocarbon-solubletracer compound is selected from the group consisting of a halogenatedaromatic compound, a halogenated cycloalkane or a halogenated aliphaticcompound.
 16. An emulsion according to claim 11, wherein the at leastone hydrocarbon-soluble tracer compound is selected from the groupconsisting of a halogenated aromatic compound, a halogenated cycloalkaneor a halogenated aliphatic compound.
 17. An emulsion according to claim11, wherein the discontinuous organic liquid phase of the emulsioncontains more than one tracer compound.